The Ortho and Para States of Water

The H20 molecule has yet more special characteristics; for example, its ortho and
para states. These terms stem from two special states of dihydrogen (H 2) - a
molecule composed of two hydrogen atoms, each with one proton (or nucleus)
and one electron orbiting it. The rotational direction of the proton is defined by
its spin value, +1/2 or -1/2. If the nuclear spins are in opposite directions, the H 2
molecule is known as para; and if the vector sum of the spins is non-zero, it is
ortho. The same definitions apply to the H20 molecule according to whether or
not the nuclear spins of the two H atoms are in opposite directions.
This distinction is very interesting. Through it we can show that there are
three times as many ways of attaining the ortho state than the para. This implies
that the intensities of the spectral lines corresponding to rotational and
vibrational-rotational transitions of the two types of H 20, occurring at slightly
different wavelengths, are in the ratio 3:1. This allows us to measure, spectroscopically,
the relative quantities of each of the two types. The relationship
between the abundances of the two types depends upon the temperature at
which the molecule forms - and no mechanism can later modify it. Measuring
the orthoipara ratio of water therefore provides a direct indication of the
temperature at which the molecule formed. Later (in Chapter 4) we shall further
examine the interesting implications of such measurements for the study of
water in celestial bodies, with particular emphasis on comets.
Among the gases of the earth's atmosphere there are two which are
spectroscopically very active: water vapour and carbon dioxide, while the
two principal gases, N2 and 02 , are practically inert. Both H20 and C02 have
very rich spectra, and H20, with its strong dipole moment, combines a very
intense rotational spectrum with strong vibrational-rotational bands around
2.7 and 6.2 j.im. C02 however, with no dipole moment, has no purely
rotational spectrum, but has intense vibrational-rotational bands, especially
around 15 and 4.25 jam. As a result, the Earth's atmosphere is opaque to most
infrared radiation from outside, with the exception of a few infrared windows,
traditionally labelled J to N, around 1.25 jam, 1.65 |.im, 2.2 j.im, 3.5 |.im, 4.5 |.im
and 10 |.im. In the ultraviolet, the atmosphere is equally opaque, but for
different reasons: solar UV, when absorbed, causes photodissociation of
molecules such as 0 2 and 03 . Only the region of 0.4-0.9 jam is practically
transparent, causing the warming of the Earth's surface and constituting
almost the total solar energy received. It is possible to observe the domains of
the near and mid-infrared from the ground due to the atmospheric windows,
but not the far or submillimetre domains, so astronomers have recourse to
measurement in space or from aircraft. During the 1980s and 1990s, NASA's
The ortho and para states of water 25
flying observation platforms (on a Lear Jet and the Kuiper Airborne
Observatory) carried out high-altitude observations, the KAO reaching a height
of 14 km. However, the best data have been obtained from Earth orbit -
notably by the ISO satellite. Since then, other satellites (Submillimeter
Wavelength Astronomical Satellite, and Odin) have concentrated on the
particularly intense submillimetre water transition at 557 GHz (A. = 538 jam).
The European Herschel satellite, to be launched in 2007, will take up the baton
from ISO with a high-resolution all-sky survey in the submillimetre.
Figure 1.13. Absorption in the Earth's atmosphere, from ultraviolet to infrared. When
absorption equals 1; the atmosphere is completely opaque, as is the case for the ultraviolet
and far-infrared domains. If it is near zero, the atmosphere is transparent; for example, in
the visible. There are several atmospheric windows in the near and mid-infrared.
Figure 1.14. Transmission through the Earth's atmosphere in the radio, millimetre and
submillimetre domains. Most atmospheric absorption is due to H20 and its isotopes.
The windows used by astronomers are found at 80-110 Ghz (around /. = 3 mm), 1 30-
180 Ghz (/. = 2 mm), and 200-280 Ghz (/. = 1.3 mm). Observations in the submillimetre
windows (610-690 Ghz, /. = 460 |.im, and 800-890 Ghz, /. = 350 j.im) require an
excellent high-altitude site and very dry atmospheric conditions.